Treatment of hydrocarbon oils



C. P. DUBBS TREATMENT 0F HYDROCRBON OILS Filed Feb. 27. 1931 enmrwlk WENN@ Aug. 2n, 19m,

RQNUNNBJNNUUKRN RDN Patented Aug, 2i, 1934:-

Uairao stares LWLZM PATENT OFFICE 1,971,214 TREATMENT OF HYDROCARBON OILS Application February 27, 1931, Serial No. 518,617

` 1 Claim. (Cl. 196-66) This invention relates to the treatment of hydrocarbon oils and refers more particularly to the production of low boiling point hydrocarbon mixtures, suitable for use as fuel in internal combustion engines, from hydrocarbon mixtures of relatively higher boiling point by the application of heat and pressure, with the production of materially increased yields of hydrocarbons of gasoline boiling point range over that coml@ monly encountered in cracking processes.

More specifically, the invention contemplates the utilization of reactive gas mixtures containing hydrogen in preponderating amounts, produced electrically, the hydrogen and hydrogencontaining gases so produced being utilized to inuence the course of the cracking reaction in the general direction of increased yields of compounds of relatively high hydrogen content boiling within the range of gasoline.

In a specic embodiment of the invention, a heavy hydrocarbon oil,` typified by a crude oil from which compounds of gasoline boiling point range have been removed by ordinary non-cracking distillation meth-ods, may be fed to a heating 5 zone of a cracking unit, either directly or after heat exchange and contact 'relation with the products of the cracking reaction undergoing treatment in a fractionating zone of said unit; the heated products from said heating zone may be introduced into an enlarged reaction zone for further reaction and wherein an electric arc, resistance unit, or other means may be disposed, adapted to activate the vaporous portions of the products of reaction after their admixture with previously activated gases or gaseous mixtures. 'I'he reaction zone products may then be passed to suitable dephlegmating apparatus from whence vapors may issue to cooling, condensing and collecting equipment of the process, and unvapor- 40 ized dephlegmated portions of said products are returned to the heating zone for further treatment. i

Other and further objects and advantages of the invention will'become apparent from the following description and accompanying diagrammatic drawing showing a side-elevational view of one form of apparatus in which the invention may be carried out.

Referring tothe drawing, raw oi1 charging stock, such as topped crude, maybe passedfrom a. suitable source of supply (not shown) through 'a line 1, controlled by valve 2, to a pump3 for discharge into a line 4 leading from said pump.

' As desired, said raw feed may be passed through a, line 5, controlled by valve 6, communicating,

with said line 4, and introduced into a fractionator or dephlegmatory 26 wherein the products of reaction are undergoing treatment, to bring said raw feed in heat exchange relation with such products, cooling said products and incidentally fractionating certain portions ofsaid feed, and after such heat exchange relation, passing from said fractionator, together with the insuiiiciently converted, relatively heavy portions of the products of reaction through a line 9, controlled by a valve 10, to a line 7, controlled by a valve 8, also in communication with said line 4 and through which said raw oil feed may be fed directly in event it is desired to by-pass said fractionator 26. The raw oil feed and/or mixture of raw oil feed and reflux condensate from said fractionator may be discharged from said line 7 into a pump 11, from whence they may be passed through a line 12, controlled by valve 13 into a tubular heating element 14 disposed within 75 a suitable furnace 15 of any desired type. Activated gas mixtures, produced in a manner to be hereinafter more fully described, may be introduced into feed line 12 through a line 16, controlled by valve 17.

The products to be heated within heating element 14 may be subjected to any desired temperature condition therein, depending on the character of the oil and the ultimate desired product. Such temperature may range from about 850 F., to about 950 F., more or less, while the pressures utilized therein may be of the order of 500 to 3000 pounds per square inch.

After subjection to the desired temperature and pressure within said heating element, the heated oils may be passed from said heating element through a line 18, controlled by valve 19 into an enlarged reaction zone wherein further reactions may occur, and wherein a pressure substantially the same as that employed in 95 heating element 14 may be maintained. I -have found that due to the activated state of the gases and gaseous mixtures produced by my process, I am enabled to employ a Wide range of pressures and that hydrogenation may be l elected within relatively low limits and yet effect the desired reactions to produce the ultimate low boiling point product sough In order to further promote, progress and accelerate the reactions occurring Within chamber 20, there may be disposed therein, preferably at or substantially near the vapor outlet thereof, a suitable activating or energizing means, such as electrodes 21 and 21', or any other desired activating means, between or into which gaseous n0 mixtures from a line 22, controlled by valve 23 Incondensable and fixed gases produced in the (said line 22 being in communication with line 16 process and collecting within said primary reheretofore referred to), and/or hydrogen from a ceiver 32 may be discharged from said receiver line 58, controlled by valve 59, or a mixture of 32 through a line 39', controlled by valve 40, to hydrogen and gaseous mixtures, may be introa pump 41 (should the pressure diierential en- 8G duced into said chamber, to produce a condition tail the necessity of use of said pump), and disfavorable to the interaction of hydrogen 01' charged from said pump through a line 42, conhydrogen-containing gases with the vapors protrolled by valve 43 into a secondary receiver or duced by the initial cracking of said raw oil inactivating unit 44; or if it be unnecessary or untroduced into said reaction zone. As stated, other desirable to subject such gases to treatment withactivating means may be eInDlOYed, Which may in said unit 44, such gases may be recycled from take the form of metal plates suspended within said iine 42 leading to said unit 44, through a 1ine Drcper spacing in Said Chamber, having aDI'ODer 45, controlled by valve 46, to a pump 47, comeleCtriC potential Supplied thereto t0 DrOClUCe municating withv line 16 previously referred to, electric discharges Of Varying intensiti7 11D t0 and leading to said reaction chamber 20 through com- 90 including a continuous arc. These electrodes may munication with iine 22 hereinbefore referred to, preferably be of such metals as tungsten; or, if and wherein such gases may be subjected, as predesired, Snell actiVatiOn may be effected by means viously described, to the activating action of the 0f heating grids 0f reSiStanCe Wires t0 a Suitable electrodes 21 and 2l disposed within said chamdeeree of incandescence- When such resistance ber; or, if Such activating action be undesirable grids comprise tungsten or metals of similar char- 0iunneeessary, such gases may be passed directly acteristics, there is produced adissociation of hyfrom Said line 16 to Seid line 12 through which drogen molellles resulting in a Substantial for' raw oil and reux condensate may be passing to matn 0f hydrogen in the a'iioimo or reactivo heating element 14, as previously described. state, approximately equivalent amounts 0f In addition to the incondensable gases pro- 100 atomic hydrogen being adsorbed 0n the surface duced in the process and passed into said chamof the wires and discharged or repelled into the ber 44, extraneous gases, Similaiin ehametei-iesurrounding vapor space of said chamber. tie te such ineondensabie gases may also be in Heavieri uriVaPoriZod iiquid residual products troduced into said chamber through a line 50, may 'De WlthdraWn from Chamber 20 through a controlled by valve 51; or any desired amount 105 line 6o, controlled by valve 61, for passage-tol` ef meieeuiar hydrogen (depeilding upon the ex.. storage, or for utilization elsewhere. Vapors may tent of hydregeneltien te be effected and the hy be Withdrawn from Said oiiuiriber through imo 24 drogen content of the activated gaseous mixtures controlled by valve 25, and introduced into fracproduced lu said Chamber) may be introduced tionaior 2o which may prefelahly ho maintained into said chamber, either alone or admixed with 110 after which the cooled products may pass under a substantially reduced pressure from that extraneous lueondeusable gases, through a lino maintained within said reaction chamber, which 53, Controlled by valve 52 Any excess of gases pressure may be oi the order of from 10o to 50o or liquid products within said chamber 44 may pounds p er Sonore lllch depollolllg upon. the pros' be withdrawn therefrom through a line 54, consur? maintained Wlthm Said Toaohoh ohilhher trolled by valve 55. The pressures utilized within while the temperatures employed therein will be salu Chamber may be substantially lower than proportloholie tolhe telhporo'turos. employed and those employed Within said receiver 32 and fraclhe pressorres lltlllzed Wll'hlh heohhg element 14 tionator 26, and are preferably of the order of and reaction chamber 20, and will be dependent about 20 pounds por square lnoh or less or sub also upon the amount of raw charging oil which stanually subtmosphorlo. 12o moy be lod therethrough Ill.passlhg through To produce activated gas mixtures, either alone said fractionator, the vapors will effect heat exor admlxed with hydrogen or hydrogomoontalm oha'hge wllh the lhcomlllg lo'w olla'lglhg. oll pass' ing gases, the gaseous mixtures introduced into lhg iihel'elihllollgh' as pevlolsly dsol'lbed and chamber 44 are subjected to activation by means the hghl" lllloohoellse por lons. o saldyapolls of any typical electrical connections 49 and 49 125 may then be passed from said fractionator disposed Within Said chamber which means may lilllliollglh o hle 27 ocomlillolled hytvolv zdto a be substantially similar to those utilized within Sud ab c?? Sseereitholo'tse llnl aollllelowllll a reaction chamber 20, heretofore described. On lolalcemalntlne Within said fractlonator as subjection to the electrical treatment within said desired C 001m g of the vapors is effected Witm chamber, the molecular hydrogen will be dissoin Said condenser with resultant condensa ciated into reactive forms of either monatomic tion of the produots uqueable at the tem or triatomc nature, and the excess of hydrogen peratures and pressures maintained therein contained within the incondensable gases will be brought to its activated state. The resultant acthrough a une 3o, controlled by valve 31 into a tivated gaseous mixture may then be withdrawn 135 from said chamber through a line 56 controlled rimary receiver 32, from which the liquefied hyrocarbon mixtures of approximately motor fuel by Yalve 57' lo lllle 45. topllmp 47. and thence boiling point rango may be removed through a to lme 16 for introduction mto reaction chamber line 33, controlled by a valve 34. To control the 2o or Passage Wllh the chalglllg oll' helhg fed quality of the vapors issuing from fractionator lo hoahhg olemehi 14 as plevlollsly oescl'llled 140 26, as well as to further aid in controlling and Ih Some, lhstahoes the ajVelage o olhposlhoh of maintaining a relatively constant temperature the gas mixtures to he activated Within ohojmbor within said fractionator, any desired amount of 44 may approximate that of methane Which 1S the liquid Within Said primary receiver 32 ap.. usual when the extraneous gas employed is natproximating motor fuel boiling point, may be Ural gaS- In Such event, the passage 0f the gas 14 withdrawn from said receiver and introduced into miXture through a high temperature electric are, said fractionator through a line 36, controlled with pressures in chamber 44 being maintained at by valve 37, to a pump 35, and passed from said points in the neighborhood of 20 millimeters of pump through a line 38, controlled by valve 39 mercury absolute, there may be produced subinto the upper portion of said f-ractionator. stantial amounts of acetylene and hydrogen in the approximate volumetric ratio of i to 3. This gas mixture may be transmitted by pump 47 to reaction chamber 20, wherein reactions of a character tending toward hydrogenation with increased production of gasoline fractions may be eected. In addition to the reactions of hydrogenation, the reactions between the components of the activated mixture, such as are exemplied by acetylene, tends to produce hydrocarbons of a generally more pronounced aromatic nature. The reactions producing the mixture of acetylene and hydrogen mentioned proceeds at great velocity in an electric arc, but is reversed in succeeding portions of the equipment if immediate cooling is not practiced. In another method of producing similar mixtures, gas mixtures approximating the composition of methane may be heated by external means in chamber 44 to temperatures of the order of about 1750 F.. more or less, under pressures of about 10 to 30 millimeters absolute, suincient space being provided to allow the reaction to progress to completion.

Of course, if desired, a plurality of chambers 44 may be utilized and employed alternately. While certain units may be producing activated hydrogen, in others the resistance wires may be cooled to allow the escape of adsorbed hydrogen and render the wires capable of further dissociation action when reheated again to the proper point of incandescence.

As an example of one operation of the process and results obtainable thereby, a 25 gravity topped crude is fed to the heating element of the pro/cess at the rate of approximately 1000 barrels per day. When cracking this stock without the use of activating means within reaction chamber 20 or the introduction of activated gas mixtures,

pounds per square inch, and considerable excess of activated hydrogen is employed within the vapor space of the reaction chamber, the yield of hydrocarbons of gasoline boiling point range will be increased to 70% and the quality of the residual oil produced greatly improved as regards carbon content and applicability for processing to produce homogeneous fuel residues and lubricating stocks.

`I claim as my invention:-

In a hydrocarbon oil cracking process of the character wherein the .oil is heated to cracking temperature under pressure while owing in a restricted stream through a heating zone and thence discharged into an enlarged unheated reaction zone maintained under cracking conditions of temperature and pressure and wherein vapors are' evolved from the heated oil; the improvement which comprises maintaining a. region of electrical activation in the vapor space of the reaction zone, subjecting incondensable gases produced in the process to a preliminary activation treatment. then introducing the gases into the reaction zone adjacent the electrical activating region and activating the same therein, reacting the thus activated hydrogen with the oil vapors in the reaction zone, and removing the treated vapors from the reaction zone for fractionating and condensation.

- CARBON P. DUBBS. 

